CN1159210C - Process for preparing V catalyst used to prepare low-temp sulfuric acid - Google Patents
Process for preparing V catalyst used to prepare low-temp sulfuric acid Download PDFInfo
- Publication number
- CN1159210C CN1159210C CNB011341092A CN01134109A CN1159210C CN 1159210 C CN1159210 C CN 1159210C CN B011341092 A CNB011341092 A CN B011341092A CN 01134109 A CN01134109 A CN 01134109A CN 1159210 C CN1159210 C CN 1159210C
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- low
- vanadium
- temperature
- vanadium catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a preparation method of a vanadium catalyst for low temperature sulfuric acid production, which belongs to the field of catalyzing techniques. The vanadium catalyst for low temperature sulfuric acid production is prepared by the method that low temperature activating agents, soluble metal cesium salts, sodium salts and phosphorus contained compounds are added, and different adjuvant adding methods are used. The vanadium catalyst for low temperature sulfuric acid production, which is prepared by the method, has good low temperature activity, and is suitable for the upper parts of the first sections and the double conversion parts of converters of sulfuric acid production devices with double conversion and double absorption processes.
Description
Technical field: the invention belongs to catalysis technical field, be specifically related to a kind of manufacture method of V catalyst used to prepare low-temp sulfuric acid.
Background technology: vanadium catalyst is used for sulfuric acid production plant with SO
2Oxidation conversion is SO
3General traditional vanadium catalyst is vanadium-potassium (sodium)-silicon system, two kinds of middle warm type and low temperature modifications are arranged, and middle temperature type vanadium catalyst generally is used for, two, three section of convertor, and the service temperature general requirement is higher than 420 ℃, be no more than 600 ℃, it is active to have middle preferably temperature; Low-temperature type vanadium catalyst generally is used for one section top of convertor and four sections, five sections, and the service temperature general requirement is higher than 410 ℃, has better low temperature activity, helps improving SO in the sulfuric acid conversion device
2Be converted into SO
3Total conversion rate.In the sulfuric acid production plant of double conversion and double absorption flow process combination loading traditional in, low-temperature type vanadium catalyst, can make SO
2Final transformation efficiency reaches 99.5%.
The existing manufacture method of vanadium catalyst:
Vanadium catalyst is generally vanadium-potassium-silicon system at present, and low-temperature type vanadium catalyst is vanadium-potassium-sodium-silicon system.Manufacture method be with raw material diatomite through the making beating, acid treatment, overanxious washing and drying make terra silicea purificata; KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes satisfactory KVO
3With KOH mixing solutions (being called for short vanadium water), then vanadium water is made V with the sulfuric acid neutralization
2O
5And K
2SO
4The colloidal precipitation thing will mix in the adding rollers such as colloidal precipitation thing and auxiliary agent, terra silicea purificata to scale, rolls closely, becomes the plasticity-material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.Vanadium catalyst with this method preparation can satisfy the needs of gas washing in SA production substantially, but uses traditional low-temperature type vanadium catalyst will satisfy SO
2It is difficult that total conversion rate reaches more than 99.8%.
Summary of the invention: the objective of the invention is to propose a kind of manufacture method of low-temperature type vanadium catalyst, this catalyzer has higher low temperature active and thermostability than traditional low-temperature type vanadium catalyst, can satisfy higher SO
2Total conversion rate needs.
The low-temperature type vanadium catalyst that the inventive method is produced has better low-temperature catalyzed performance than traditional low-temperature type vanadium catalyst, low 20～40 ℃ of the more traditional vanadium catalyst of combustion initiation temperature, service temperature can be reduced to 380～390 ℃ from 410～420 ℃, this catalyzer is substituted low-temperature type vanadium catalyst be used for gas washing in SA production, can make the SO of the sulfuric acid apparatus of double conversion and double absorption flow process
2Final transformation efficiency reaches 99.8%, and reduced the service temperature of one section of convertor, helps high density SO
2Conversion, adapted to that sulfuric acid apparatus maximizes and the development of acid production with sulphur, use this catalyzer at the convertor latter end, improved the total conversion rate in the convertor, reduced SO in the tail gas
2Concentration, satisfied the environmental requirement of increasingly stringent.
The present invention is achieved like this, and by adding the low-temperature activation agent, improves the low temperature active of vanadium catalyst, reduces combustion initiation temperature.It mainly comprises following content: the low-temperature activation agent is soluble metal cesium salt, sodium salt, P contained compound, and addition manner is for adding when mixed grind or it being joined in the vanadium water; The catalyst formulation weight percent is V
2O
55.0～8.5% K
2O/V
2O
52.5～4.5 Na
2SO
41.0～15.0% Cs
2SO
41.0～15.0% P
2O
51.0～5.0% all the other be diatomite.
The used soluble metal cesium salt of the present invention can be a kind of in cesium sulfate, cesium carbonate, the cesium nitrate, also can be two or three mixture wherein; Sodium salt is a sodium sulfate; P contained compound can be a kind of in phosphoric acid, ammonium phosphate, the sodium acid phosphate salt; Diatomite can be a kind of in Linqu, Shandong diatomite, northeast long white diatomite, Shengxian County, Zhejiang diatomite and the Yunnan Xun Dian diatomite.
The vanadium catalyst of the present invention preparation is applicable to the one section top and the two transfer part branches of convertor of the sulfuric acid production plant of double conversion and double absorption flow process.
Embodiment: further specify content of the present invention below in conjunction with embodiment:
Embodiment 1-1
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
413.7% P
2O
51.0% all the other be diatomite; Adopt traditional processing technology, Linqu, Shandong diatomite through wet concentration, acid treatment, overanxious washing and drying, is made the Shandong terra silicea purificata; KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 2.7 KVO
3With KOH mixing solutions (being called for short vanadium water), then a certain amount of vanadium water is made V with the sulfuric acid neutralization
2O
5And K
2SO
4The colloidal precipitation thing is to scale with colloidal precipitation thing and Na
2SO
4, H
3PO
4, mix in the adding roller such as Shandong terra silicea purificata, add water-powered roller and compress closely, become the plasticity-material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.
Embodiment 1-2
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
48.0% Cs
2SO
42.0% P
2O
51.0% all the other be diatomite; Adopt traditional processing technology.
Embodiment 1-3
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
46.0% Cs
2SO
44.0% P
2O
51.0% all the other be diatomite; Adopt traditional processing technology.
Embodiment 1-4
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
48.0% Cs
2SO
42.0% P
2O
51.0% all the other be diatomite; Employing adds the low-temperature activation agent in vanadium water.
Embodiment 1-5
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
44.0% Cs
2SO
410.0% P
2O
51.0% all the other be diatomite; Employing adds the low-temperature activation agent in vanadium water.
Embodiment 1-6
Sample prescription V
2O
57.0% K
2O/V
2O
52.7 Na
2SO
42.0% Cs
2SO
410.0% P
2O
51.0% all the other be diatomite; Employing adds the low-temperature activation agent in vanadium water.
Sample test
Catalyst sample: granularity is
The active testing condition:
Convertor: adopt the jacketed type single tube reactor, its caliber is
The temperature thermocouple cover
Pipe is positioned at the center of convertor, and its caliber is
Catalyzer loading amount: 30ml;
Catalyst grain size: 6～6.5mm;
Space velocity: 3600h;
Air inlet SO
2Percent by volume: be air surplus in the of 10 ± 1%;
System pressure: normal pressure;
Active detected temperatures: 390 ℃, 410 ℃;
Heat resisting temperature and time: 600 ℃ of 5h;
With SO
2Transformation efficiency represent active height.
Active testing the results are shown in table one, and wherein sample 1-1 is traditional low-temperature type vanadium catalyst, and sample 1-2,1-3,1-4,1-5,1-6 are ultralow warm type vanadium catalyst
Table one active testing result
| The sample example | Active (heat-resisting back SO 2Transformation efficiency) % | Relative value | ||
| 390℃ | 410℃ | 390℃ | 410℃ | |
| 1-1 | 22.0 | 38.1 | 1 | 1 |
| 1-2 | 29.5 | 47.4 | 1.34 | 1.24 |
| 1-3 | 27.9 | 48.9 | 1.27 | 1.28 |
| 1-4 | 28.1 | 47.4 | 1.27 | 1.24 |
| 1-5 | 29.5 | 45.6 | 1.34 | 1.20 |
| 1-6 | 32.5 | 56.1 | 1.48 | 1.47 |
Can find out that by test result the low temperature active of the ultralow warm type vanadium catalyst of employing the inventive method preparation shows that apparently higher than traditional low-temperature type vanadium catalyst the performance of the vanadium catalyst that the present invention prepares is significantly improved, and can satisfy higher SO
2The total conversion rate requirement.
Claims (1)
1. the manufacture method of a V catalyst used to prepare low-temp sulfuric acid, by adding the low-temperature activation agent, improve the low temperature active of vanadium catalyst, reduce combustion initiation temperature, it is characterized in that the low-temperature activation agent is cesium sulfate, sodium sulfate, phosphoric acid, the weight percent of catalyzer is V
2O
55.0～8.5% K
2O/V
2O
52.5～4.5 Na
2SO
41.0～15.0% Cs
2SO
41.0～15.0% P
2O
51.0～5.0% all the other be diatomite; The manufacture method of catalyzer be with diatomite through wet concentration, acid treatment, filtration washing and drying, make terra silicea purificata, by said ratio, KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes KVO
3With the KOH mixing solutions, be called for short vanadium water, then with Cs
2SO
4, Na
2SO
4, H
3PO
4Join in the vanadium water, make V with the sulfuric acid neutralization again
2O
5And K
2SO
4The colloidal precipitation thing, will the colloidal precipitation thing and terra silicea purificata add in the roller and mix, add water-powered roller and compress closely, become the plasticity-material, again through extrusion, drying, roasting, sieve and packaging process is made vanadium catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011341092A CN1159210C (en) | 2001-10-30 | 2001-10-30 | Process for preparing V catalyst used to prepare low-temp sulfuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011341092A CN1159210C (en) | 2001-10-30 | 2001-10-30 | Process for preparing V catalyst used to prepare low-temp sulfuric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1342601A CN1342601A (en) | 2002-04-03 |
| CN1159210C true CN1159210C (en) | 2004-07-28 |
Family
ID=4672241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011341092A Expired - Fee Related CN1159210C (en) | 2001-10-30 | 2001-10-30 | Process for preparing V catalyst used to prepare low-temp sulfuric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1159210C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299973C (en) * | 2002-12-11 | 2007-02-14 | 南化集团研究院 | New Vanadium catalyst for low-temperature sulfuric acid production and its prepn |
| CN101041131B (en) * | 2006-03-20 | 2010-09-08 | 襄樊市精信催化剂有限责任公司 | Wide temperature type sulfur dioxide oxidation system producing aulfuric acid and the preparing method |
| CN101462048B (en) * | 2008-06-21 | 2011-08-24 | 康喆 | Vanadium catalyst containing tungsten for producing acid by oxidation and preparation method thereof |
| CN102350367B (en) * | 2011-08-30 | 2013-08-14 | 开封市三丰催化剂有限责任公司 | Production method of sulfuric acid catalyst by oxidizing sulfur dioxide |
| CN103506143A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion |
| CN104741110A (en) * | 2015-03-25 | 2015-07-01 | 襄阳市精信催化剂有限责任公司 | Process for preparing sulfuric acid catalyst by oxidation of sulfur dioxide |
| CN105126861A (en) * | 2015-09-07 | 2015-12-09 | 吉林省天元硅藻科技有限公司 | Sulfuric acid catalyst prepared through middle and low temperature hydrogen sulfide wetting method and preparation method therefor |
| CN111036242A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Vanadium-based catalyst for preparing sulfuric acid by wet conversion |
| CN109759052B (en) * | 2019-02-14 | 2021-12-07 | 襄阳市精信催化剂有限责任公司 | Preparation method of catalyst for preparing sulfuric acid by oxidizing sulfur dioxide |
-
2001
- 2001-10-30 CN CNB011341092A patent/CN1159210C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1342601A (en) | 2002-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1159210C (en) | Process for preparing V catalyst used to prepare low-temp sulfuric acid | |
| CN104043477B (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN105148982A (en) | Transition metal-containing aluminosilicate zeolite | |
| CN111804347B (en) | Preparation method of Janus particles and application of Janus particles in cyclohexene hydration process | |
| CN111135859A (en) | Long-chain normal paraffin hydroisomerization catalyst and preparation method thereof | |
| CN111375431A (en) | Solid acid catalyst, preparation method thereof and application thereof in esterification ester exchange reaction | |
| CN115011323A (en) | Viscosity reducer for hydrothermal cracking of heavy oil and preparation method and application thereof | |
| CN1226184C (en) | Prepn of active phase of vanadium catalyst for sulfuric acid production | |
| CN1322918C (en) | Vanadium catalyst for preparing sulfuric acid by wet conversion and its preparation method | |
| CN101757938A (en) | Method for preparing low-temperature vanadium catalyst in for sulphuric acid production | |
| CN102319571B (en) | Catalyst for catalyzing hydrocracking of biomass oil and preparation method and application thereof | |
| CN1233548C (en) | Medium-temperature vanadium catalyst for sulfuric acid production and its prepn | |
| CN1299973C (en) | New Vanadium catalyst for low-temperature sulfuric acid production and its prepn | |
| CN101249433B (en) | Preparation method of rare earth metal oxide/zirconia catalyst | |
| CN106582833A (en) | Methyl methoxyacetate catalyst | |
| CN102093206B (en) | Method for preparing levulinic acid by hydrolyzing sucrose by using nickel sulfate on silica gel as catalyst | |
| CN103657697B (en) | A kind of vanadium catalyst for gas washing in SA production and preparation method thereof | |
| CN105413670B (en) | It is a kind of to prepare solid acid catalyst of butylene and preparation method thereof for n-butanol dehydration | |
| CN106311299A (en) | Vanadium catalyst used for producing sulfuric acid by high-density reforming gas and preparation method thereof | |
| CN109453758B (en) | Denitration catalyst and preparation method thereof | |
| CN101757939A (en) | Low-temperature vanadium catalyst in sulphuric acid production | |
| CN112588313A (en) | Fe-Cu-SSZ-13 catalyst and preparation method thereof | |
| CN112717990A (en) | Cu-SSZ-13@ Fe with core-shell structurexOyCatalyst and preparation method thereof | |
| CN109513453A (en) | A kind of application of metal oxide@clay-based solid-acid material and its catalysis biomass hydrolysis | |
| CN100337749C (en) | Molecular sieve catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040728 Termination date: 20131030 |